US4431525AExpiredUtility
Three-catalyst process for the hydrotreating of heavy hydrocarbon streams

Assignee: STANDARD OIL CO INDIANAPriority: Apr 26, 1982Filed: Apr 26, 1982Granted: Feb 14, 1984
Est. expiryApr 26, 2002(expired)· nominal 20-yr term from priority
Inventors:Albert L. Hensley, Jr.Leonard M. Quick
C10G 2300/107B01J 35/60B01J 35/615B01J 35/67B01J 35/635B01J 35/647
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Claims
Abstract

There is disclosed a process for hydrotreating a heavy hydrocarbon stream containing metals, asphaltenes, nitrogen compounds, and sulfur compounds to reduce the contents of these contaminants. The process comprises contacting said stream in the presence of hydrogen and under suitable hydrotreating conditions in sequence with a first catalyst in a first reaction zone, a second catalyst in a second reaction zone, and a third catalyst in a third reaction zone. The first catalyst comprises a Group VIB metal and/or a Group VIII metal on a porous inorganic oxide support; the second catalyst consists essentially of at least one hydrogenation metal selected from Group VIB deposed on a support material comprising alumina; and the third catalyst comprises a hydrogenating component comprising molybdenum, chromium, and cobalt on a large-pore, catalytically-active alumina. Each catalyst has specific physical properties.
Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A process for hydrotreating a heavy hydrocarbon stream containing metals, asphaltenes, nitrogen compounds, and sulfur compounds to reduce the contents of metals, asphaltenes, nitrogen compounds, and sulfur compounds in said stream, which process comprises contacting said stream in a first reaction zone in the presence of hydrogen and under suitable hydrotreating conditions with a first catalyst comprising a hydrogenating component selected from the group consisting of a metal of Group VIB of the Periodic Table of Elements, a metal of Group VIII, and a mixture thereof deposed upon a porous inorganic oxide support, said hydrogenating component being present in the elemental form, as the oxide, as the sulfide, or mixtures thereof and said first catalyst having a surface area of about 120 m 2  /gm to about 400 m 2  /gm, a pore volume of about 0.7 cc/gm to about 1.5 cc/gm, and an average pore diameter within the range of about 12.5 nm (125 Å) to about 35 nm (350 Å) to provide an effluent from said first reaction zone; contacting said effluent from said first reaction zone in a second reaction zone in the presence of hydrogen and under suitable hydrotreating conditions with a second catalyst consisting essentially of at least one active original hydrogenation metal selected from Group VIB of the Periodic Table of Elements deposed on a catalytically-active support comprising alumina, said metal of Group VIB being in the elemental form, as the oxide, as the sulfide, or a mixture thereof, and said second catalyst having a surface area within the range of about 150 m 2  /gm to about 300 m 2  /gm, a majority of its pore volume in pore diameters within the range of about 8 nm (80 Å) to about 13 nm (130 Å), and a pore volume within the range of about 0.4 cc/gm to about 0.9 cc/gm to provide an effluent from said second reaction zone; and contacting said effluent from said second reaction zone in the presence of hydrogen and under suitable hydrotreating conditions with a third catalyst comprising (1) the metals of molybdenum, chromium, and cobalt, (2) their oxides, (3) their sulfides, or (4) mixtures thereof deposed on a large-pore, catalytically-active alumina, said third catalyst having a pore volume within the range of about 0.4 cc/gm to about 0.8 cc/gm, a surface area within the range of about 150 m 2  /gm to about 300 m 2  /gm, and an average pore diameter within the range of about 10 nm (100 Å) to about 20 nm (200 Å). 
     
     
       2. The process according to claim 1, wherein said stream is a member selected from the group consisting of atmospheric petroleum residua, vacuum petroleum residua, tar sands oils, tar sands residua, and liquids obtained from coal. 
     
     
       3. The process of claim 1, wherein said conditions that are employed in the first reaction zone and the second reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 454° C. (850° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB), and wherein said conditions that are employed in the third reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 438° C. (820° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB). 
     
     
       4. The process according to claim 1, wherein said hydrogenating component of said first catalyst is a metal of Group VIB of the Periodic Table of Elements. 
     
     
       5. The process according to claim 1, wherein the metal of Group VIB of the Periodic Table of Elements of said second catalyst is molybdenum. 
     
     
       6. The process according to claim 1, wherein said molybdenum of said third catalyst is present in an amount within the range of about 5 wt % to about 15 wt %, calculated as MoO 3  and based upon the total weight of said third catalyst, said chromium of said third catalyst is present in an amount within the range of about 5 wt % to about 20 wt %, calculated as Cr 2  O 3  and based upon the total weight of said third catalyst, and said cobalt of said third catalyst is present in an amount within the range of about 0.1 wt % to about 5 wt %, calculated as CoO and based upon the total weight of said third catalyst. 
     
     
       7. The process according to claim 1, wherein said second catalyst has less than 40% of its pore volume in pores having diameters within the range of 5 nm (50 Å) to about 8 nm (80 Å), about 15% to about 65% of its pore volume in pores having diameters within the range of about 8 nm (80 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 13 nm (130 Å), and less than 15% of its pore volume in pores having diameters that are larger than 13 nm (130 Å). 
     
     
       8. The process according to claim 1, wherein said third catalyst has about 0% to about 10% of its pore volume in pores having diameters that are smaller than 5 nm (50 Å), about 30% to about 80% of its pore volume in pores having diameters within the range of about 5 nm (50 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 15 nm (150 Å), and about 0% to about 10% of its pore volume in pores having diameters that are larger than 15 nm (150 Å). 
     
     
       9. The process according to claim 2, wherein said conditions that are employed in the first reaction zone and the second reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 454° C. (850° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB), and wherein said conditions that are employed in the third reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 438° C. (820° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB). 
     
     
       10. The process according to claim 4, wherein the metal of Group VIB of the Periodic Table of Elements of said second catalyst is molybdenum. 
     
     
       11. The process according to claim 4, wherein said molybdenum of said third catalyst is present in an amount within the range of about 5 wt % to about 15 wt %, calculated as MoO 3  and based upon the total weight of said third catalyst, said chromium of said third catalyst is present in an amount within the range of about 5 wt % to about 20 wt %, calculated as Cr 2  O 3  and based upon the total weight of said third catalyst, and said cobalt of said third catalyst is present in an amount within the range of about 0.1 wt % to about 5 wt %, calculated as CoO and based upon the total weight of said third catalyst. 
     
     
       12. The process according to claim 5, wherein said molybdenum of said third catalyst is present in an amount within the range of about 5 wt % to about 15 wt %, calculated as MoO 3  and based upon the total weight of said third catalyst, said chromium of said third catalyst is present in an amount within the range of about 5 wt % to about 20 wt %, calculated as Cr 2  O 3  and based upon the total weight of said third catalyst, and said cobalt of said third catalyst is present in an amount within the range of about 0.1 wt % to about 5 wt %, calculated as CoO and based upon the total weight of said third catalyst. 
     
     
       13. The process according to claim 7, wherein said third catalyst has about 0% to about 10% of its pore volume in pores having diameters that are smaller than 5 nm (50 Å), about 30% to about 80% of its pore volume in pores having diameters within the range of about 5 nm (50 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 15 nm (150 Å), and about 0% to about 10% of its pore volume in pores having diameters that are larger than 15 nm (150 Å). 
     
     
       14. The process according to claim 10, wherein said molybdenum of said third catalyst is present in an amount within the range of about 5 wt % to about 15 wt %, calculated as MoO 3  and based upon the total weight of said third catalyst, said chromium of said third catalyst is present in an amount within the range of about 5 wt % to about 20 wt %, calculated as Cr 2  O 3  and based upon the total weight of said third catalyst, and said cobalt of said third catalyst is present in an amount within the range of about 0.1 wt % to about 5 wt %, calculated as CoO and based upon the total weight of said third catalyst. 
     
     
       15. The process according to claim 14, wherein said metal of Group VIB of the Periodic Table of Elements of said first catalyst is molybdenum and is present in an amount within the range of about 8 wt % to about 12 wt % MoO 3 , calculated as MoO 3  and based upon the weight of said first catalyst and wherein said molybdenum of said second catalyst is present in an amount within the range of about 0.5 wt % to about 5 wt %, calculated as MoO 3  and based upon the weight of said second catalyst. 
     
     
       16. The process according to claim 15, wherein said second catalyst has less than 40% of its pore volume in pores having diameters within the range of 5 nm (50 Å) to about 8 nm (80 Å), about 15% to about 65% of its pore volume in pores having diameters within the range of about 8 nm (80 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 13 nm (130 Å), and less than 15% of its pore volume in pores having diameters that are larger than 13 nm (130 Å). 
     
     
       17. The process according to claim 15, wherein said stream is a member selected from the group consisting of atmospheric petroleum residua, vacuum petroleum residua, tar sands oils, tar sands residua, and liquids obtained from coal. 
     
     
       18. The process according to claim 16, wherein said third catalyst has about 0% to about 10% of its pore volume in pores having diameters that are smaller than 5 nm (50 Å), about 30% to about 80% of its pore volume in pores having diameters within the range of about 5 nm (50 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 15 nm (150 Å), and about 0% to about 10% of its pore volume in pores having diameters that are larger than 15 nm (150 Å). 
     
     
       19. The process according to claim 17, wherein said conditions that are employed in the first reaction zone and the second reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 454° C. (850° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB), and wherein said conditions that are employed in the third reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 438° C. (820° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB). 
     
     
       20. The process according to claim 18, wherein said stream is a member selected from the group consisting of atmospheric petroleum residua, vacuum petroleum residua, tar sands oils, tar sands residua, and liquids obtained from coal. 
     
     
       21. The process according to claim 20, wherein said conditions that are employed in the first reaction zone and the second reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 454° C. (850° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB), and wherein said conditions that are employed in the third reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 438° C. (820° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB). 
     
     
       22. A process for the hydrotreating of a heavy hydrocarbon stream containing metals, asphaltenes, nitrogen compounds, and sulfur compounds to reduce the contents of metals, asphaltenes, nitrogen compounds and sulfur compounds in said stream, which process comprises contacting said stream under suitable hydrotreating conditions in a first reaction zone in the presence of hydrogen with a first catalyst comprising molybdenum deposed upon a large-pore alumina, said molybdenum of said first catalyst being present in an amount of about 1 wt %, calculated as MoO 3  and based upon the weight of the said first catalyst, said first catalyst having a surface area of about 120 m 2  /gm to about 400 m 2  /gm, a pore volume of about 0.7 cc/gm to about 1.5 cc/gm, and an average pore diameter of about 12.5 nm (125 Å) to about 35 nm (350 Å), said molybdenum of said first catalyst being present as the element, as the oxide, as the sulfide, or mixtures thereof to provide an effluent from the first reaction zone; contacting said effluent from said first reaction zone in a second reaction zone under suitable hydrotreating conditions and in the presence of hydrogen with a second catalyst consisting essentially of molybdenum deposed upon a catalytically-active alumina having a pore size that is smaller than that of said first catalyst, said molybdenum of said second catalyst being present in an amount of about 10 wt %, calculated as MoO 3  and based upon the weight of said second catalyst, said molybdenum being present in the elemental form, as the oxide, as the sulfide, or mixtures thereof and said second catalyst having a surface area within the range of about 150 m 2  /gm to about 300 m 2  /gm, a majority of its pore volume in pore diameters within the range of about 8 nm (80 Å) to about 13 nm (130 Å), and a pore volume within the range of about 0.4 cc/gm to about 0.9 cc/gm, said second catalyst having less than 40% of its pore volume in pores having diameters within the range of about 5 nm (50 Å) to about 8 nm (80 Å), about 15% to about 65% of its pore volume in pores having diameters within the range of about 8 nm (80 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 13 nm (130 Å), and less than 15% of its pore volume in pores having diameters that are greater than 13 nm (130 Å), to provide an effluent from said second reaction zone; and contacting said effluent from said second reaction zone under suitable hydrotreating conditions and in the presence of hydrogen in a third reaction zone with a third catalyst comprising about 1.3 wt % cobalt, calculated as CoO and based upon the weight of said third catalyst, about 10 wt % molybdenum, calculated as MoO 3  and based upon the weight of said third catalyst, and about 10 wt % chromium, calculated as Cr 2  O 3  and based upon the weight of said third catalyst, deposed upon a large-pore, catalytically-active alumina, said third catalyst having a pore volume within the range of about 0.4 cc/gm to about 0.8 cc/gm, a surface area within the range of about 150 m 2  /gm to about 300 m 2  /gm, and an average pore diameter within the range of about 10 nm (100 Å) to about 20 nm (200 Å) and said third catalyst having about 0% to about 10% of its pore volume in pores having diameters that are smaller than 5 nm (50 Å), about 30% to about 80% of its pore volume in pores having diameters within the range of about 5 nm (50 Å) to about 10 nm (100 Å), about 10% to about 50% of its pore volume in pores having diameters within the range of about 10 nm (100 Å) to about 15 nm (150 Å), and about 0% to about 10% of its pore volume in pores having diameters that are larger than 15 nm (150 Å) to provide a hydrotreated product containing contents of metals, asphaltenes, nitrogen compounds, and sulfur compounds that are lower than those of the corresponding components in said stream. 
     
     
       23. The process according to claim 22, wherein said stream is a member selected from the group consisting of atmospheric petroleum residua, vacuum petroleum residua, tar sands oils, tar sands residua, and liquids obtained from coal. 
     
     
       24. The process according to claim 23, wherein said conditions that are employed in the first reaction zone and the second reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 454° C. (850° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB), and wherein said conditions that are employed in the third reaction zone comprise a hydrogen partial pressure within the range of about 6,900 kPa (1,000 psia) to about 20,700 kPa (3,000 psia), an average catalyst bed temperature within the range of about 371° C. (700° F.) to about 438° C. (820° F.), an LHSV within the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of about 356 m 3  /m 3  (2,000 SCFB) to about 2,671 m 3  /m 3  (15,000 SCFB).
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